WO2019054508A1 - Structure annulaire de particules métalliques, structure annulaire de particules métalliques revêtues d'isolant et composition - Google Patents

Structure annulaire de particules métalliques, structure annulaire de particules métalliques revêtues d'isolant et composition Download PDF

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Publication number
WO2019054508A1
WO2019054508A1 PCT/JP2018/034299 JP2018034299W WO2019054508A1 WO 2019054508 A1 WO2019054508 A1 WO 2019054508A1 JP 2018034299 W JP2018034299 W JP 2018034299W WO 2019054508 A1 WO2019054508 A1 WO 2019054508A1
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Prior art keywords
particle
metal
particles
metal particle
insulating
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PCT/JP2018/034299
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English (en)
Japanese (ja)
Inventor
高野橋　寛朗
中林　亮
直矢 栃下
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Priority to KR1020207006853A priority Critical patent/KR102296364B1/ko
Priority to EP18857014.7A priority patent/EP3682986B1/fr
Priority to US16/646,569 priority patent/US11352504B2/en
Priority to JP2019542325A priority patent/JP6938651B2/ja
Priority to CA3075792A priority patent/CA3075792C/fr
Priority to CN201880055121.2A priority patent/CN111065473B/zh
Publication of WO2019054508A1 publication Critical patent/WO2019054508A1/fr
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q15/00—Devices for reflection, refraction, diffraction or polarisation of waves radiated from an antenna, e.g. quasi-optical devices
    • H01Q15/02—Refracting or diffracting devices, e.g. lens, prism
    • H01Q15/10—Refracting or diffracting devices, e.g. lens, prism comprising three-dimensional [3D] array of impedance discontinuities, e.g. holes in conductive surfaces or conductive discs forming artificial dielectric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3045—Treatment with inorganic compounds
    • C09C1/3054—Coating
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • the present invention relates to a metal particle annular structure, an insulating material coated metal particle annular structure, and a composition.
  • metamaterials are materials that artificially form metals, dielectrics, magnetic substances, and the like with a structure smaller than the wavelength of incident light and artificially change the permittivity and permeability of the medium.
  • metal is an artificial substance that behaves like a substance in nature not to electromagnetic waves containing light. For example, as it shows a property that can not be realized with conventional materials, such as enabling the light propagation direction to be bent in the direction showing a negative refractive index, it is intended to expand the ability to artificially manipulate the light propagation. It attracts expectations and is the subject of intense research and development.
  • the above-mentioned metamaterial is an artificial material in which a large number of micro-nanometer scale resonator antenna elements responsive to electromagnetic waves including light are integrated, and the optical characteristics of the material are artificially designed by appropriately designing the resonator antenna elements. It has the property of being able to
  • the size of the metal microresonator is about 1 ⁇ 4 to 1/10 of the wavelength of the electromagnetic wave acting as a metamaterial (hereinafter referred to as “operating wavelength”). For example, for an operating wavelength shorter than microwaves, micrometres in the order of micrometers and nanometers are required in the size of the microstructure for metal microresonators. Because the microfabrication difficulty required to fabricate metal microresonators rapidly increases in response to the required fineness, the operating wavelength of many metamaterials is millimeter scale microwaves or better It is considered to be a long wavelength range. Most metamaterial cases that are demonstrated are also of such wavelength range.
  • SRR structure split-ring resonator structure
  • the SRR structure is formed of, for example, a conductor provided with a gap or a split portion such as a notch in an annular conductive path.
  • top-down approach and bottom-up approach as a micromaterial processing technology of metamaterial including the fabrication method of SRR structure.
  • the top-down method is a method of processing a fine structure with high accuracy by a human being precisely controlling all processes including an exposure pattern, such as a photolithography method.
  • a top-down method a method of repeating a series of steps of resist application, electron beam drawing, metal thin film deposition, and lift-off has been proposed and demonstrated (see, for example, Non-Patent Document 2).
  • the bottom-up method is a method of self-organizing shape making use of the property of the substance so that water molecules gather to form snow crystals or the living body is shaped by itself. It is. Although low-cost, large-scale and high-speed machining can be performed, the degree of freedom in the accuracy and machining shape is limited.
  • a method of producing a metamaterial structure using a bottom-up method a method utilizing formation of various ordered structures by applying an external magnetic field to particles dispersed in a fluid has been proposed. If the core part is paramagnetic or ferromagnetic and the peripheral part is a diamagnetic object smaller than the core part, a minute structure in which several peripheral parts are arranged is formed near the equator of the core part. This structure functions as a microresonator for the above-described metamaterial (see, for example, Patent Document 1).
  • a method that combines a top-down approach and a bottom-up approach has also been proposed.
  • a pattern is formed by electron beam drawing of polymethyl methacrylate (PMMA) resist material on a silicon substrate.
  • PMMA polymethyl methacrylate
  • a metal thin film is vacuum deposited on the substrate, and the remaining PMMA film is removed to form a metal ribbon structure.
  • the metal ribbon is bent to form a ring structure which is vertically supported on the surface of the silicon substrate.
  • This ring structure is made to function as one resonator antenna which comprises a metamaterial (for example, refer nonpatent literature 3).
  • Non-Patent Document 2 is a method of adopting an approach in which a two-dimensional structure is laminated one by one to produce a three-dimensional structure by adopting a conventional semiconductor fine processing technology. . Therefore, there is a problem that structural errors are easily accumulated when producing a three-dimensional structure. Furthermore, it is difficult to produce large area, large volume metamaterial structures because of the large amount of time it takes to make.
  • Patent Document 1 requires application of a magnetic field when producing a microstructure to function as a resonator, and requires a special manufacturing apparatus.
  • the application direction of the magnetic field is one direction, the resonators can be arranged only in a certain direction. Therefore, although it functions as a metamaterial for electromagnetic waves in a particular direction, it has a strong anisotropy that the function is lost when the incident direction changes.
  • the size of metamaterials that can be adapted by this method is submicron limit, and it is not possible to provide nanometer-scale metamaterial materials that operate with visible light and ultraviolet light.
  • Non-Patent Document 3 can form a three-dimensional structure, it requires a plurality of semiconductor microfabrication techniques. Therefore, as with the method disclosed in Non-Patent Document 1, there is also a problem that it takes a lot of time to execute the manufacturing process, and it is necessary to manufacture a large-area, large-volume metamaterial structure. With difficulties.
  • the problem to be solved by the present invention is to provide a novel metal particle annular structure as a nanometer scale resonator structure which can function as a metamaterial three-dimensionally, an insulation coated metal particle annular structure value, and a composition. It is to do.
  • Metal particle ring comprising: an insulating support (B) comprising a particle connection structure in which a plurality of particles are connected; and a plurality of metal particles (A) annularly arranged around the insulating support (B) Structure (C).
  • the particle connection structure comprises a structure in which first insulating particles (a) and second insulating particles (b) are alternately connected in a chain, and the plurality of metal particles (A) are The metal particle annular structure (C) according to the above [1], which is disposed around one of the first insulating particle (a) or the second insulating particle (b).
  • the metal particle (A) is a conductor selected from the group consisting of gold, silver, copper, lead, zinc, tin, iron and aluminum, any one of the above [1] to [6]
  • the metal particle (A) is a core-shell type metal particle (As) whose surface is covered with a first insulating material, according to any one of the above [1] to [7].
  • Metal particle annular structure (C) as described.
  • a novel metal particle annular structure as a nanometer scale resonator structure which can function as a metamaterial three-dimensionally, an insulating coated metal particle annular structure value, and a composition. .
  • FIG. 1 is an example of a schematic view of a metal particle cyclic structure according to the present invention, which comprises three anion particles 1a and one cation particle 1b disposed between the two anion particles 1a.
  • a metal particle annular structure comprising: an insulating support consisting of a particle connection structure; and six negatively charged metal particles 1A annularly arranged on the surface of cationic particles 1b in the insulating support is there. It is a figure which shows another example of the metal particle cyclic structure by this invention.
  • FIG. 1 is an example of a schematic view of a metal particle cyclic structure according to the present invention, which comprises three anion particles 1a and one cation particle 1b disposed between the two anion particles 1a.
  • a metal particle annular structure comprising: an insulating support consisting of a particle connection structure; and six negatively charged metal particles 1A annularly arranged on the surface of cationic particles 1b in the insulating support is there.
  • FIG. 1 is an example of a
  • FIG. 2 is an example of a schematic view of a metal particle cyclic structure according to the present invention, which comprises five anion particles 2a and five cation particles 2b disposed between the three anion particles 2a.
  • Metal particle provided with an insulating support consisting of a particle connection structure and six negatively charged metal particles 2A annularly arranged on the surface of each particle of the cationic particles 2b in the insulating support It is a cyclic structure. It is a figure which shows an example which took out a part of metal particle cyclic structure by this invention.
  • FIG. 3 is a view showing the structure of six negatively charged metal particles A (1A or 2A) annularly disposed on the surface of the cationic particles b (1b or 2b) in FIGS.
  • FIG. 16 is a SEM image of the insulating support (B-1) composed of the particle connection structure produced in Reference Example 5.
  • FIG. 7 is a SEM image of the gold particle cyclic structure (C-1) produced in Example 1.
  • the metal particle cyclic structure (C) of the present invention comprises an insulating support (B) comprising a plurality of metal particles (A) and a particle connection structure in which a plurality of particles are connected, and the metal particles (A) Are arranged in a ring around the insulating support (B).
  • the metal particle (A) of the present invention is at least one conductor selected from the group consisting of gold, silver, copper, lead, zinc, tin, iron and aluminum. It is preferable that it is at least 1 sort (s) chosen from gold, silver, and copper from a viewpoint of the characteristic expression as a metamaterial of the metal particle cyclic structure (C) comprised from this metal particle (A).
  • the average diameter of the metal particles (A) is preferably 5 nm or more and 200 nm or less.
  • the metal particle cyclic structure (C) comprised from this metal particle (A) expresses the characteristic as a metamaterial.
  • the transparency of the metal particle cyclic structure (C) comprised from this metal particle (A) becomes favorable, and the industrial application field spreads.
  • the average diameter is more preferably 10 nm or more and 100 nm or less, still more preferably 15 nm or more and 80 nm or less.
  • the average diameter of the metal particles (A) can be measured from SEM images, dynamic light scattering, and the like.
  • the metal particles (A) in the present invention are preferably core-shell type metal particles (As) coated with an insulating material (first insulating material).
  • core-shell type metal particle means a structure in which the surface of the metal particle (A) as a core (core) is coated with a first insulating material as a shell (shell).
  • the average thickness of the first insulating material is preferably 1 nm or more and 80 nm or less.
  • the plurality of metal particles (A) can be prevented from being in direct contact with each other.
  • the metal particle cyclic structure (C) composed of the metal particles (A) is not preferable because it becomes difficult to exhibit metamaterial properties.
  • the metal particle annular structure (C) composed of the metal particles (A) can exhibit excellent metamaterial properties. More preferably, it is 2 nm or more and 50 nm or less, and still more preferably 2 nm or more and 20 nm or less.
  • the first insulating material is preferably at least one selected from the group consisting of metal oxides, metal nitrides, metal sulfides, phosphates, and organic compounds.
  • the metal oxide, the metal nitride, and the metal sulfide may have an organic group.
  • the first insulating material as a metal oxide or phosphate
  • the metal oxide is preferably at least one selected from silicon oxide, titanium oxide, zinc oxide, zirconium oxide, iron oxide, niobium oxide, cerium oxide and nickel oxide.
  • silicon oxide is preferable because it is relatively easy to coat the metal particles (A) to produce core-shell type metal particles (reaction control is easy).
  • a phosphate porous calcium phosphate etc. can be used suitably.
  • the low molecular weight compound of molecular weight 1000 or less and the high molecular compound of number average molecular weight 1000 or more can be mentioned.
  • an organic compound having an interaction with the metal particles (A) is preferable because it can stably and firmly prevent the plurality of metal particles (A) from being in direct contact with each other.
  • the organic compound having an interaction with the metal particles (A) include a silane coupling agent, silicone resin, urethane resin, fluorocarbon resin, silicone-acrylic resin, polyethylene glycol, block copolymer of polyethylene glycol and polypropylene glycol, Polyvinyl alcohol etc. can be mentioned.
  • silane coupling agent what has an amino group, a thiol group, an epoxy group, a (meth) acryloyl group, a phenyl group etc., interaction with a metal particle (A) is selected large preferably.
  • the first insulating material of the shell is a metal oxide, metal nitride, metal sulfide, phosphate, preferably in the presence of metal particles (A)
  • metal particles (A) can be obtained by reacting the precursor of the first insulating material (eg, metal complex salt, alkoxy metal, etc.).
  • the first insulating material of the shell is an organic compound
  • a precursor of the first insulating material in the presence of the metal particles (A) It can be obtained by reacting (for example, a vinyl monomer, a condensation monomer, an addition polymerization monomer, etc.) or depositing an organic compound on the surface of a metal particle (A) using a difference in solubility.
  • the insulating support (B) comprising the particle connection structure of the present invention is formed by connecting insulating particles by Coulomb interaction, van der Waals interaction, covalent bond, hydrogen bond or the like.
  • insulating particles by Coulomb interaction, van der Waals interaction, covalent bond, hydrogen bond or the like.
  • connection means a state in which particles are linked by Coulomb interaction, van der Waals interaction, covalent bond, hydrogen bond or the like.
  • the insulating particles are made of at least one selected from the group consisting of metal oxides, metal nitrides, metal sulfides, and organic compounds.
  • the metal oxide, the metal nitride, and the metal sulfide may have an organic group.
  • the metal oxide examples include silicon oxide, titanium oxide, zinc oxide, zirconium oxide, iron oxide, niobium oxide, cerium oxide, nickel oxide and the like. Moreover, as a metal in a metal nitride and a metal sulfide, iron, cobalt, nickel, lead, zinc, copper etc. can be illustrated.
  • the organic compound used as the insulating particles preferably, a high molecular compound having a number average molecular weight of 1000 or more can be mentioned.
  • the polymer compound all synthetic resins and natural resins can be used, and acrylic resin, silicone resin, urethane resin, fluorine resin, silicon-acrylic resin, epoxy resin, alkyd resin, vinyl resin, unsaturated polyester resin And chlorinated rubber and the like.
  • the average diameter of the insulating particles is preferably 5 nm or more and 600 nm or less. From the viewpoint of shape stability, more preferably 10 nm or more and 200 nm or less, and from the viewpoint of optical characteristics (transparency), it is preferably 10 nm or more and 100 nm or less.
  • the insulating support (B) composed of the particle connection structure of the present invention is preferably composed of 2 or more and 30 or less spherical particles from the viewpoint of stably arranging a plurality of metal particles (A) in a ring shape. . Furthermore, it is preferable to be composed of three or more and ten or less spherical particles from the viewpoint of optical properties (transparency).
  • the particle connection structure when the particle connection structure is constituted by three spherical particles using Coulomb interaction, as shown in FIG. 1, the particle connection structure includes two anion particles 1a and two anions. It can consist of one cationic particle 1b disposed between particles 1a. In this case, each of the metal particles 1A can be disposed on the surface of the cation particle 1b by negatively charging it to form anion particles.
  • the plurality of metal particles 1A can be disposed on the surface of the anion particle 1a by charging each of the metal particles 1A positively to form cation particles.
  • the anionic particle 1a is not particularly limited as long as it is an anionic particle having a negative charge, and examples thereof include negatively charged metal oxides, metal nitrides, metal sulfides and organic compounds. From the viewpoint of simplicity of diameter control and cost, anionic metal oxide particles, anionic group-containing polymer latex and the like can be preferably used. Among them, anionic silica particles and anionic polymer latex are preferably used.
  • the cationic particle 1b is not particularly limited as long as it is a cationic particle having a positive charge, but, for example, metal oxides, metal nitrides, metal sulfides, and organic compounds obtained by cationizing the particle surface may be mentioned.
  • metal oxides, metal nitrides, metal sulfides, and organic compounds obtained by cationizing the particle surface may be mentioned.
  • Can. From the viewpoint of simplicity of particle size control and cost, cationic metal oxide particles, cationic group-containing polymer latex and the like can be preferably used. Above all, it is preferable to use cationic silica fine particles and cationic polymer latex from the viewpoint of simplicity of particle diameter control and cost.
  • the number of metal particles (A) annularly disposed around one insulating particle in the insulating support (B) comprising the particle connection structure is 3 or more and 30 or less. Is preferred. By setting the number of metal particles (A) to three or more, unique metamaterial properties (optical effects) can be exhibited. When the number of metal particles (A) exceeds 30, the metal particle cyclic structure (C) to be produced becomes large, which is not preferable because the transparency is impaired.
  • the number of metal particles (A) is more preferably 3 or more and 20 or less, and still more preferably 4 or more and 10 or less.
  • annular form will not be specifically limited, A ring shape, elliptical shape, the shape which has an unevenness
  • FIG. 1 is an example of a schematic view of a metal particle cyclic structure according to the present invention, which comprises three anion particles 1a and one cation particle 1b disposed between the two anion particles 1a.
  • a metal particle annular structure comprising: an insulating support consisting of a particle connection structure; and six negatively charged metal particles 1A annularly arranged on the surface of the cationic particles 1b in the insulating support It is shown.
  • FIG. 2 is an example of another schematic view of the metal particle cyclic structure according to the present invention, and two cation particles 2b disposed between three anion particles 2a and the three anion particles 2a. And five negatively charged metal particles 2A annularly arranged on the surface of each particle of the cationic particles 2b in the insulating support. The metal particle annular structure is shown.
  • FIG. 3 is a schematic view showing a structure of six negatively charged metal particles A annularly arranged on the surface of the cation particle b in FIG. 1 and FIG. 2.
  • the metal particles (A) are preferably arranged in a ring without contacting each other, and as the form of the arrangement, for example, the metal particles (A) are spaced
  • the metal particles may be arranged in an array such that the surfaces of the metal particles are in contact with the insulating material of the core-shell type metal particles coated with the insulating material.
  • the metal particle cyclic structure (C) of the present embodiment strongly exerts the function as a metamaterial because the metal particles (A) are not in contact with each other.
  • the distance between the adjacent metal particles (A) is preferably 0.1 to 200 nm, more preferably 1 to 100 nm, and still more preferably 5 to 50 nm, from the viewpoint of being excellent in the function as a metamaterial.
  • the distance between at least one set of adjacent metal particles (A) contained in the metal particle annular structure (C) of the present embodiment preferably satisfies the above range, and the distance between all adjacent metal particles satisfies the above range. Is more preferred.
  • the distance between the metal particles (A) means the distance between the outer ends of the adjacent metal particles (if covered, the distance between the outer ends of the metal particles excluding the covering portion).
  • the spacing between the metal particles (A) can be measured, for example, by an SEM image, a TEM image, or an AFM image.
  • the metal particles (A) are preferably arranged in a ring shape having a diameter of 15 to 1000 nm from the viewpoint of exerting the function as a metamaterial strongly. More preferably, they are arranged in an annular shape having a diameter of 30 to 500 nm.
  • circular shape which a metal particle (A) arranges means the diameter of the circle
  • the largest diameter among the diameters of the annular shape measured from any three metal particles (A) is used.
  • the metal particles (A) and the insulating support (B) composed of particle connection structures interact with each other.
  • the interaction include inter-ionic interaction (ionic bond), hydrogen bond, covalent bond, dipole interaction, London dispersion force (van der Waals force), charge transfer interaction (electron transfer between two molecules) And ⁇ - ⁇ interaction (trans ring interaction, dispersion force acting between aromatic rings), hydrophobic interaction, and the like.
  • the above interaction is achieved by at least one combination of the metal particles (A) and the insulating support (B) composed of particle connection structures, which are included in the metal particle cyclic structure (C) of the present embodiment It is more preferable that all the metal particles (A) and the insulating support (B) composed of the particle connection structure interact in the above-mentioned manner.
  • the metal particle cyclic structure (C) in the present invention can be obtained by mixing the insulating support (B) comprising the particle connection structure and the metal particles (A).
  • the insulating support (B) comprising the particle connection structure in the present invention is preferably produced using a micromixer that mixes two or more types of fluids.
  • a micromixer that mixes two or more types of fluids.
  • an insulating support (B) composed of a particle connection structure a production example in which two anion particles and one cation particle disposed between the two anion particles are described. Do.
  • the raw material of anion particles such as anion latex
  • a micromixer for mixing two or more kinds of fluids
  • the raw material of cationic particles eg, cationic latex
  • the number of anion particles: cation particle number 2 : Supply so as to be 1.
  • the insulating support (B) composed of a particle connection structure is composed of two anion particles of the above-mentioned example and one cation particle disposed between the two anion particles.
  • the insulating support (B) composed of the particle connection structure in the present invention has not only the interaction of van der Waals force, covalent bond, hydrogen bond, etc., in addition to the combination of Coulomb interaction of anion particles and cation particles described above. Several particles can be connected using it.
  • the metal particles (A) mixed with the insulating support (B) composed of the particle connection structure have a surface state (zeta potential, or the like) of the metal particles (A) according to the interaction forming the particle connection structure.
  • the metal particles (A) can be firmly fixed to the insulating support (B) by controlling the functional group, the SP value, etc., which is preferable.
  • the metal particle annular structure (C) obtained by mixing the insulating support (B) composed of the particle connection structure and the metal particles (A) is subjected to heat treatment, light irradiation, microwave treatment, etc.
  • the metal particles (A) can be firmly immobilized on the insulating support (B), which is preferable.
  • the metal particles (A) are the insulating support (B). It is particularly preferable because it can hold the immobilized state.
  • the second insulating material used to obtain the insulating material-coated metal particle annular structure (F) of the present invention is preferably used to produce the core-shell type metal particles (As) in the present invention described above.
  • the first insulating material can be mentioned.
  • the insulating material-coated metal particle annular structure (F) of the present invention is a metal particle instead of the metal particle (A) in the same method as the core-shell type metal particle (As) in the present invention described above. It can be obtained by using the cyclic structure (C).
  • composition As a composition of this embodiment, the composition containing the said metal particle cyclic structure (C) and water and / or the organic solvent is mentioned, for example.
  • the organic solvent include alcohols such as methanol, ethanol, propanol, isopropanol and butanol; ethers such as dimethyl ether and diisopropyl ether; alkanes such as pentane and hexane; cyclic alkanes such as cyclohexane; ethyl methyl ketone; Dichloromethane, tetrahydrofuran, acetone, acetic acid, ethyl acetate, 1,4 dioxane, benzene, toluene, acetonitrile, dimethyl formaldehyde, dimethyl sulfoxide, and the like.
  • composition containing the metal particle cyclic structure (C) of the present invention and water and / or an organic solvent may be used as it is as a coating agent, or a composition (E) comprising a resin (D) described later You may use it at the time of doing.
  • the content of the metal particle cyclic structure (C) is from 0.00001 to 99 based on the weight of the composition. It is preferably 9 wt%, more preferably 0.001 to 50 wt%.
  • the content of the metal particle cyclic structure (C) is smaller than 0.00001% by weight, it is difficult to exhibit the function as a metamaterial when used as a coating agent, which is not preferable.
  • the metal particle cyclic structure (C) of the present invention can also be used as a composition (E) comprising a resin (D).
  • a resin which can be used for the composition (E) of the present invention all synthetic resins and natural resins can be used.
  • the form thereof may be a pellet or a form dissolved or dispersed in a solvent.
  • a resin paint for coating is most preferable.
  • resin coatings include oil-based paints, lacquers, solvent-based synthetic resin paints (acrylic resins, epoxy resins, urethane resins, fluorocarbon resins, silicone-acrylic resins, alkyd resins, amino alkyd resins, vinyl Resin system, unsaturated polyester resin system, chlorinated rubber system etc., water based synthetic resin paint (emulsion system, water based resin system etc.), solvent free synthetic resin paint (powder paint etc.), inorganic paint, electrical insulating paint etc. be able to.
  • solvent-based synthetic resin paints acrylic resins, epoxy resins, urethane resins, fluorocarbon resins, silicone-acrylic resins, alkyd resins, amino alkyd resins, vinyl Resin system, unsaturated polyester resin system, chlorinated rubber system etc.
  • water based synthetic resin paint emulsion system, water based resin system etc.
  • solvent free synthetic resin paint solvent free synthetic resin paint (powder paint etc.)
  • components which are usually added to a paint or a molding resin depending on the use and the method of use such as a thickener, Leveling agent, thixotropic agent, antifoaming agent, freezing stabilizer, matting agent, crosslinking reaction catalyst, pigment, curing catalyst, crosslinking agent, filler, anti-skin agent, dispersing agent, wetting agent, antioxidant, rheology Control agent, antifoaming agent, film forming aid, rust inhibitor, dye, plasticizer, lubricant, reducing agent, preservative, mildew agent, deodorant, anti-yellowing agent, antistatic agent or charge control
  • the agents and the like can be selected and combined according to the respective purposes.
  • the metal particle annular structure (C) or composition (E) of the present invention is a paint, a finish of a building material, an adhesive, an adhesive, a paper processing agent or a woven fabric, a non-woven finish, a sealing agent, an adhesive It can be widely used as an agent, ink, coating material, casting material, elastomer, foam and plastic raw material, fiber treatment agent and the like.
  • composition (E) of the present invention an organic / inorganic composite in the form of a film, a sheet, a fiber or a molded product can be formed.
  • the thickness of the coating film, the minimum reflectance, the average reflectance, and the refractive index were calculated using a reflection spectrophotometer (FE3000: manufactured by Otsuka Electronics Co., Ltd.).
  • Micromixer Slit-Plate Mixer LH2 (manufactured by Airfeld Co., Ltd.) was used as a micromixer.
  • the configuration of the mixing plate in the micro mixer is as follows. Mixing plate LH2-50 / 50 ⁇ m, 10 + 10 slits Aperture plate LH2-50 ⁇ m, 2 mm
  • a mixed solution of 150 g of butyl acrylate, 165 g of methyl methacrylate, 3 g of acrylic acid, and 13 g of a reactive emulsifier (trade name "ADECARIA SOAP SR-1025, manufactured by Asahi Denka Co., Ltd., solid content 25% by mass aqueous solution)
  • a mixed solution of 40 g of a 2% by mass aqueous solution of ammonium persulfate and 1900 g of ion-exchanged water was simultaneously added dropwise over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C. Further, as heat curing, the temperature in the reaction vessel was kept at 80 ° C. and stirring was continued for about 2 hours.
  • the mixture was then cooled to room temperature and filtered through a 100 mesh wire mesh to obtain a polymer emulsion particle water dispersion having a solid content of 8.3% by mass and a number average particle diameter of 62 nm.
  • the emulsion was adjusted to a concentration of 2 ⁇ 10 12 / ml with distilled water to obtain an anionic polymer emulsion particle water dispersion (a-1).
  • the resulting silica-coated gold particle aqueous dispersion was distilled water under the conditions of a circulation flow rate of 840 ml / min and a pressure of 0.04 Mpa using Microfiber UF, ACP-0013D (Asahi Kasei Co., Ltd.) of hollow fiber type.
  • the purification by 50% filtration was repeated four times to obtain an aqueous dispersion of silica-coated gold particles (A-1s) having an average particle diameter of 50 nm and a concentration of 8.9 ⁇ 10 10 cells / ml.
  • the obtained aqueous dispersion of silica-coated gold particles (A-1s) was dropped on a silicon wafer and then dried under reduced pressure to perform SEM observation (FIG. 4).
  • A-2s silica-coated gold particles
  • the resulting silver particle water dispersion was subjected to 50 ⁇ l of distilled water using a hollow fiber type Microser UF, ACP-0013D (Asahi Kasei Corp.), a circulation flow rate of 840 ml / min, and a pressure of 0.04 Mpa. After repeating% filtration and purification four times, distilled water was added to adjust the concentration to 8.9 ⁇ 10 10 particles / ml, and a number average particle diameter of 40 nm and a silver particle water dispersion (A-3) were obtained.
  • a mixed solution of 150 g of butyl acrylate, 165 g of methyl methacrylate, 3 g of acrylic acid, and 13 g of a reactive emulsifier (trade name "ADECARIA SOAP SR-1025, manufactured by Asahi Denka Co., Ltd., solid content 25% by mass aqueous solution)
  • a mixed solution of 40 g of a 2% by mass aqueous solution of ammonium persulfate and 1900 g of ion-exchanged water was simultaneously added dropwise over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C. Further, as heat curing, the temperature in the reaction vessel was kept at 80 ° C. and stirring was continued for about 2 hours.
  • the mixture was then cooled to room temperature and filtered through a 100 mesh wire mesh to obtain a polymer emulsion particle water dispersion having a solid content of 8.3% by mass and a number average particle diameter of 62 nm.
  • the emulsion was adjusted to a concentration of 1% by mass with distilled water to obtain an anionic polymer emulsion particle water dispersion (a-4).
  • the anionic particle (a-1) aqueous dispersion prepared in Reference Example 1 with the micromixer and the cationic particle (b-1) aqueous dispersion prepared in Reference Example 3 are each 5.0 mL / min using a syringe pump Mixed solution discharged from a silicone tube with an inner diameter of 1 mm and a length of 106 mm connected to the outlet side of the micro mixer is dropped onto a silicon wafer cooled with liquid nitrogen and flash frozen, and then dried under reduced pressure in a frozen state As a result of SEM observation, formation of a structure in which three particles were connected was confirmed (FIG. 5).
  • Example 1 The anionic particle (a-1) water dispersion prepared in Reference Example 1 with the micromixer and the cationic silica particle (b-1) water dispersion prepared in Reference Example 3 were each 5.0 mL / ml using a syringe pump.
  • the silica-coated gold particles (A-1 s) prepared in Reference Example 7 were stirred with a magnetic stirrer by using a magnetic stirrer to stir the mixture, which was supplied in minutes and discharged from a silicone tube with an inner diameter of 1 mm and a length of 106 mm connected to the micro mixer outlet side.
  • the reaction liquid (C-1) was obtained by dropwise addition to 100 mL of the aqueous dispersion for 10.1 seconds.
  • the obtained reaction solution (C-1) was dropped on a silicon wafer, dried under reduced pressure, and observed by SEM. As a result, formation of a gold particle annular structure in which gold particles were annularly arranged was confirmed (FIG. 6) ).
  • the reaction liquid (C-1) obtained by the above method was coated with 2.0 g of a white plate glass substrate having an area of 5 cm 2 and a thickness of 2 mm, and dried at normal temperature for 24 hours. I got the substrate.
  • Example 2 The anionic particle (a-1) aqueous dispersion prepared in Reference Example 1 with the micromixer and the cationic particle (b-1) aqueous dispersion prepared in Reference Example 3 are each 5.0 mL / min using a syringe pump
  • the gold particles (A-1) dispersed in water prepared in Reference Example 6 were stirred with a magnetic stirrer and the mixture discharged from a silicone tube with an inner diameter of 1 mm and a length of 106 mm was supplied by
  • the reaction solution (B-2) was obtained by dropping it into 100 mL of the body for 10.1 seconds.
  • the reaction solution (E-2) obtained by the above method is coated on a corona-treated PET film having an area of 5 cm 2 and a thickness of 200 ⁇ m using a wire bar coater, and dried at room temperature for 24 hours (E-2)
  • a PET substrate coated with the dried coating film of Optical measurement of the PET substrate coated with the dried coating film of (E-2) showed that the average reflectance at a wavelength of 450 to 650 nm is 2.95%, and the minimum reflectance at a wavelength of 350 nm to 800 nm is 2.43% Met.
  • Example 3 The anionic particle (a-1) aqueous dispersion prepared in Reference Example 1 with the micromixer and the cationic particle (b-1) aqueous dispersion prepared in Reference Example 3 are each 5.0 mL / min using a syringe pump
  • the silica-coated gold particles (A-1s) prepared in Reference Example 7 were stirred with a magnetic stirrer by using a magnetic stirrer to stir the mixture, which was supplied from a silicone tube supplied with an inner diameter of 1 mm and a length of 106 mm.
  • the reaction mixture (C-3) was obtained by dropwise addition to 100 mL of the aqueous dispersion for 10.1 seconds.
  • the reaction solution (E-3) obtained by the above method is coated on a corona-treated PET film having an area of 5 cm 2 and a thickness of 200 ⁇ m using a wire bar coater, and dried at room temperature for 24 hours (E-3)
  • a PET substrate coated with the dried coating film of Optical measurement of this PET substrate having the dried coating film of (E-3) shows that the average reflectance at a wavelength of 450 to 650 nm is 2.70%, and the minimum reflectance at a wavelength of 350 nm to 800 nm is 2.13%. there were.
  • Example 4 The anionic particle (a-1) aqueous dispersion prepared in Reference Example 1 with the micromixer and the cationic particle (b-2) aqueous dispersion prepared in Reference Example 4 are each 5.0 mL / min using a syringe pump
  • the silica-coated gold particles (A-1s) prepared in Reference Example 7 were stirred with a magnetic stirrer by using a magnetic stirrer to stir the mixture, which was supplied from a silicone tube supplied with an inner diameter of 1 mm and a length of 106 mm.
  • the reaction mixture (C-4) was obtained by dropping it into 100 mL of the aqueous dispersion for 10.1 seconds.
  • the reaction solution (E-4) obtained by the above method is coated on a corona-treated PET film having an area of 5 cm 2 and a thickness of 200 ⁇ m using a wire bar coater, and dried at room temperature for 24 hours (E-4)
  • a PET substrate coated with the dried coating film of Optical measurement of this PET substrate having the dried coating of (E-4) showed an average reflectance of 2.52% at a wavelength of 450 to 650 nm and a minimum reflectance of 2.11% at a wavelength of 350 nm to 800 nm. there were.
  • Example 5 The anionic particle (a-1) aqueous dispersion prepared in Reference Example 1 with the micromixer and the cationic particle (b-1) aqueous dispersion prepared in Reference Example 3 are each 5.0 mL / min using a syringe pump
  • the reaction mixture (C-5) was obtained by dropwise addition to 100 mL of the aqueous dispersion for 10.1 seconds.
  • reaction solution (E-5) obtained by the above method is coated on a corona-treated PET film having an area of 5 cm 2 and a thickness of 200 ⁇ m using a wire bar coater, and dried at room temperature for 24 hours (E-5)
  • a PET substrate coated with the dried coating film of Optical measurement of the PET substrate having the dried coating film of (E-5) shows that the average reflectance at a wavelength of 450 to 650 nm is 11.35% and the minimum reflectance at a wavelength of 350 nm to 800 nm is 2.57%. there were.
  • Example 6 The anionic particle (a-1) aqueous dispersion prepared in Reference Example 1 with the micromixer and the cationic particle (b-1) aqueous dispersion prepared in Reference Example 3 are each 5.0 mL / min using a syringe pump
  • the silica-coated gold particles (A-2s) prepared in Reference Example 8 were stirred with a magnetic stirrer by using a magnetic stirrer to stir the mixture, which was supplied from the inside of the silicone tube supplied with an inner diameter of 1 mm and a length of 106 mm.
  • the reaction mixture (C-6) was obtained by dropwise addition to 100 mL of the aqueous dispersion for 10.1 seconds.
  • reaction liquid (C-6) 1.0% aqueous solution
  • PVA235 Polyvinyl alcohol
  • aqueous solution 1.0% aqueous solution
  • the reaction solution (E-6) obtained by the above method is coated on a corona-treated PET film having an area of 5 cm 2 and a thickness of 200 ⁇ m using a wire bar coater, and dried at room temperature for 24 hours (E-6)
  • a PET substrate coated with the dried coating film of Optical measurement of this PET substrate having the dried coating film of (E-6) showed an average reflectance of 2.88% at a wavelength of 450 to 650 nm and a minimum reflectance of 2.38% at a wavelength of 350 nm to 800 nm. there were.
  • Example 7 The anionic particle (a-2) aqueous dispersion prepared in Reference Example 2 with the micromixer and the cationic particle (b-3) aqueous dispersion prepared in Reference Example 5 are each 5.0 mL / min using a syringe pump
  • the silica-coated gold particles (A-1s) prepared in Reference Example 7 were stirred with a magnetic stirrer by using a magnetic stirrer to stir the mixture, which was supplied from a silicone tube supplied with an inner diameter of 1 mm and a length of 106 mm.
  • the reaction mixture (C-7) was obtained by dropping it into 100 mL of the aqueous dispersion for 10.1 seconds.
  • reaction liquid (C-7) 3.5 g of a 1.0% aqueous solution of PVA235 (Kuraray, polyvinyl alcohol) 1.0% aqueous solution is added to the obtained reaction liquid (C-7) while stirring with a magnetic stirrer, E-7).
  • the reaction solution (E-7) obtained by the above method is coated on a corona-treated PET film having an area of 5 cm 2 and a thickness of 200 ⁇ m using a wire bar coater, and dried at room temperature for 24 hours (E-7)
  • a PET substrate coated with the dried coating film of Optical measurement of the PET substrate having the dried coating film of E-7) revealed that the average reflectance at a wavelength of 450 to 650 nm is 2.75%, and the minimum reflectance at a wavelength of 350 nm to 800 nm is 2.33%.
  • the film thickness of the dry coating film determined by calculation using the least square method from the obtained reflectance data (E-6) was 150 nm, and the refractive index at a wavelength of 550 n
  • Example 8 The anionic particle (a-1) aqueous dispersion prepared in Reference Example 1 with the micromixer and the cationic particle (b-3) aqueous dispersion prepared in Reference Example 5 are each 5.0 mL / min using a syringe pump
  • the silica-coated gold particles (A-1s) prepared in Reference Example 7 were stirred with a magnetic stirrer by using a magnetic stirrer to stir the mixture, which was supplied from a silicone tube supplied with an inner diameter of 1 mm and a length of 106 mm.
  • the reaction mixture (C-8) was obtained by dropwise addition to 100 mL of the aqueous dispersion for 10.1 seconds.
  • reaction solution (E-8) obtained by the above method is coated on a corona-treated PET film having an area of 5 cm 2 and a thickness of 200 ⁇ m using a wire bar coater, and dried at room temperature for 24 hours (E-8)
  • a PET substrate coated with the dried coating film of Optical measurement of this PET substrate having the dried coating film of (E-8) showed an average reflectance of 2.45% at a wavelength of 450 to 650 nm and a minimum reflectance of 2.02% at a wavelength of 350 nm to 800 nm. there were.
  • Example 9 The anionic particle (a-1) aqueous dispersion prepared in Reference Example 1 with the micromixer and the cationic particle (b-3) aqueous dispersion prepared in Reference Example 5 are each 5.0 mL / min using a syringe pump
  • the silica-coated gold particles (A-1s) prepared in Reference Example 7 were stirred with a magnetic stirrer by using a magnetic stirrer to stir the mixture, which was supplied from a silicone tube supplied with an inner diameter of 1 mm and a length of 106 mm.
  • the reaction mixture (C-9) was obtained by dropping it into 100 mL of the aqueous dispersion for 10.1 seconds.
  • reaction solution (C-9) 100 ml of the reaction solution (C-9) is introduced into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, and the temperature in the reaction vessel is kept at 80 ° C. and stirring is carried out for about 6 hours I continued. Thereafter, the reaction solution was cooled to room temperature to obtain a reaction solution (C-9 heating). Furthermore, 3.5 g of a 1.0% aqueous solution of PVA235 (Kuraray, polyvinyl alcohol) 1.0% aqueous solution is added to the obtained reaction liquid (C-9 heating) while stirring with a magnetic stirrer, and a gold particle cyclic structure-containing PVA aqueous solution Obtained (E-9).
  • PVA235 Kelray, polyvinyl alcohol
  • the reaction solution (E-9) obtained by the above method is coated on a corona-treated PET film having an area of 5 cm 2 and a thickness of 200 ⁇ m using a wire bar coater, and dried at room temperature for 24 hours (E-9)
  • a PET substrate coated with the dried coating film of Optical measurement of this PET substrate having the dried coating film of (E-9) showed an average reflectance of 2.31% at a wavelength of 450 to 650 nm and a minimum reflectance of 1.82% at a wavelength of 350 nm to 800 nm. there were.
  • Example 10 The anionic particle (a-1) aqueous dispersion prepared in Reference Example 1 with the micromixer and the cationic particle (b-3) aqueous dispersion prepared in Reference Example 5 are each 5.0 mL / min using a syringe pump
  • the silica-coated gold particles (A-1s) prepared in Reference Example 7 were stirred with a magnetic stirrer by using a magnetic stirrer to stir the mixture, which was supplied from a silicone tube supplied with an inner diameter of 1 mm and a length of 106 mm.
  • the reaction mixture (C-10) was obtained by dropwise addition to 100 mL of the aqueous dispersion for 10.1 seconds.
  • reaction solution (C-10) 100 ml of the reaction solution (C-10) was charged into a reactor equipped with a reflux condenser, a dropping tank, a thermometer and a stirrer, and the temperature in the reaction vessel was heated to 80 ° C.
  • a reflux condenser 100 ml of the reaction solution (C-10) was charged into a reactor equipped with a reflux condenser, a dropping tank, a thermometer and a stirrer, and the temperature in the reaction vessel was heated to 80 ° C.
  • 0.5 g of aminopropyltrimethoxysilane diluted to 0.1% by mass with ethanol was added, reacted for 5 minutes, and then 2.0 g of tetraethoxysilane diluted to 1% with ethanol was added over 30 minutes
  • the solution was dropped, and the temperature in the reaction vessel was kept at 80 ° C., and stirring was continued for about 6 hours.
  • reaction solution was cooled to room temperature to obtain a reaction solution (F-10) containing an insulating material coated metal particle annular structure. Furthermore, 3.5 g of a 1.0% aqueous solution of PVA235 (Kuraray, polyvinyl alcohol) 1.0% aqueous solution is added to the obtained reaction liquid (F-10) while stirring with a magnetic stirrer, I got E-10).
  • PVA235 Kerray, polyvinyl alcohol
  • the reaction solution (E-10) obtained by the above method is coated on a corona-treated PET film having an area of 5 cm 2 and a thickness of 200 ⁇ m using a wire bar coater, and dried at room temperature for 24 hours (E-10)
  • a PET substrate coated with the dried coating film of Optical measurement of the PET substrate having the dried coating film of (E-10) showed an average reflectance of 2.25% at a wavelength of 450 to 650 nm and a minimum reflectance of 1.73% at a wavelength of 350 nm to 800 nm. there were.
  • Example 11 The anionic particle (a-1) aqueous dispersion prepared in Reference Example 1 with the micromixer and the cationic particle (b-3) aqueous dispersion prepared in Reference Example 5 are each 5.0 mL / min using a syringe pump
  • the silica-coated gold particles (A-1s) prepared in Reference Example 7 were stirred with a magnetic stirrer by using a magnetic stirrer to stir the mixture, which was supplied from a silicone tube supplied with an inner diameter of 1 mm and a length of 106 mm.
  • the reaction mixture (C-11) was obtained by dropwise addition to 100 mL of the aqueous dispersion for 10.1 seconds.
  • reaction solution (C-11) 100 ml of the reaction solution (C-11) was charged into a reactor equipped with a reflux condenser, a dropping tank, a thermometer and a stirrer, and the temperature in the reaction vessel was heated to 80.degree.
  • a reflux condenser 100 ml of the reaction solution (C-11) was charged into a reactor equipped with a reflux condenser, a dropping tank, a thermometer and a stirrer, and the temperature in the reaction vessel was heated to 80.degree.
  • 0.5 g of aminopropyltrimethoxysilane diluted to 0.1% by mass with ethanol was added, reacted for 5 minutes, and then 2.0 g of tetraethoxysilane diluted to 1% with ethanol was added over 30 minutes
  • the solution was dropped, and the temperature in the reaction vessel was kept at 80 ° C., and stirring was continued for about 6 hours. Thereafter, the reaction solution was cooled to room temperature to obtain a reaction solution (F-11).
  • reaction liquid (F-11) a 1.0% aqueous solution of PVA235 (Kuraray, polyvinyl alcohol) 1.0% aqueous solution was added to the obtained reaction liquid (F-11) while stirring with a magnetic stirrer, E-11).
  • the reaction solution (E-11) obtained by the above method is coated on a corona-treated PET film having an area of 5 cm 2 and a thickness of 200 ⁇ m using a wire bar coater, and dried at room temperature for 24 hours (E-11)
  • a PET substrate coated with the dried coating film of Optical measurement of this PET substrate having the dried coating of (E-11) showed that the average reflectance at a wavelength of 450 to 650 nm was 2.50% and the minimum reflectance at a wavelength of 350 nm to 800 nm was 1.88%.
  • Example 12 The anionic particle (a-1) aqueous dispersion prepared in Reference Example 1 with the micromixer and the cationic particle (b-3) aqueous dispersion prepared in Reference Example 5 are each 5.0 mL / min using a syringe pump
  • the silica-coated gold particles (A-1s) prepared in Reference Example 7 were stirred with a magnetic stirrer by using a magnetic stirrer to stir the mixture, which was supplied from a silicone tube supplied with an inner diameter of 1 mm and a length of 106 mm.
  • the reaction mixture (C-12) was obtained by dropwise addition to 100 mL of the aqueous dispersion for 10.1 seconds.
  • reaction solution (C-12) 100 ml of the reaction solution (C-12) was charged into a reactor equipped with a reflux condenser, a dropping tank, a thermometer and a stirrer, and the temperature in the reaction vessel was heated to 80.degree.
  • a reflux condenser 100 ml of the reaction solution (C-12) was charged into a reactor equipped with a reflux condenser, a dropping tank, a thermometer and a stirrer, and the temperature in the reaction vessel was heated to 80.degree.
  • 0.5 g of aminopropyltrimethoxysilane diluted to 0.1% by mass with ethanol was added, reacted for 5 minutes, and then 2.0 g of tetraethoxysilane diluted to 1% with ethanol was added over 30 minutes
  • the solution was dropped, and the temperature in the reaction vessel was kept at 80 ° C., and stirring was continued for about 6 hours. Thereafter, the reaction solution was cooled to room temperature to obtain a reaction solution (F-12).
  • the reaction solution (E-12) obtained by the above method is coated on a corona-treated PET film having an area of 5 cm 2 and a thickness of 200 ⁇ m using a wire bar coater, and dried at room temperature for 24 hours (E-12)
  • a PET substrate coated with the dried coating film of Optical measurement of this PET substrate having the dried coating film of (E-12) showed an average reflectance of 2.20% at a wavelength of 450 to 650 nm and a minimum reflectance of 1.50% at a wavelength of 350 nm to 800 nm. there were.
  • Example 13 The anionic particle (a-1) aqueous dispersion prepared in Reference Example 1 with the micromixer and the cationic particle (b-3) aqueous dispersion prepared in Reference Example 5 are each 5.0 mL / min using a syringe pump
  • the silica-coated gold particles (A-1s) prepared in Reference Example 7 were stirred with a magnetic stirrer by using a magnetic stirrer to stir the mixture, which was supplied from a silicone tube supplied with an inner diameter of 1 mm and a length of 106 mm.
  • the reaction mixture (C-12) was obtained by dropwise addition to 100 mL of the aqueous dispersion for 10.1 seconds.
  • reaction solution (C-12) 100 ml of the reaction solution (C-12) was charged into a reactor equipped with a reflux condenser, a dropping tank, a thermometer and a stirrer, and the temperature in the reaction vessel was heated to 80.degree.
  • a reflux condenser 100 ml of the reaction solution (C-12) was charged into a reactor equipped with a reflux condenser, a dropping tank, a thermometer and a stirrer, and the temperature in the reaction vessel was heated to 80.degree.
  • 0.5 g of aminopropyltrimethoxysilane diluted to 0.1% by mass with ethanol was added, reacted for 5 minutes, and then 2.0 g of tetraethoxysilane diluted to 1% with ethanol was added over 30 minutes
  • the solution was dropped, and the temperature in the reaction vessel was kept at 80 ° C., and stirring was continued for about 6 hours. Thereafter, the reaction solution was cooled to room temperature to obtain a reaction solution (F-13).
  • reaction liquid (F-13) while stirring with a magnetic stirrer, 3 wt% of the 1.0% by mass anionic polymer emulsion particle water dispersion (a-4) synthesized in Reference Example 10 is prepared. .5 g was added to obtain a mixed solution (E-13) of an anion latex and a gold particle cyclic structure.
  • the reaction solution (E-13) obtained by the above method is coated on a corona-treated PET film having an area of 5 cm 2 and a thickness of 200 ⁇ m using a wire bar coater, and dried at room temperature for 24 hours (E-13)
  • a PET substrate coated with the dried coating film of Optical measurement of this PET substrate having the dried coating of (E-13) showed an average reflectance of 2.51% at a wavelength of 450 to 650 nm and a minimum reflectance of 1.90% at a wavelength of 350 nm to 800 nm. there were.
  • Example 14 The anionic particle (a-1) aqueous dispersion prepared in Reference Example 1 with the micromixer and the cationic particle (b-3) aqueous dispersion prepared in Reference Example 5 are each 5.0 mL / min using a syringe pump
  • the silica-coated gold particles (A-1s) prepared in Reference Example 7 were stirred with a magnetic stirrer by using a magnetic stirrer to stir the mixture, which was supplied from a silicone tube supplied with an inner diameter of 1 mm and a length of 106 mm.
  • the reaction mixture (C-14) was obtained by dropwise addition to 100 mL of the aqueous dispersion for 10.1 seconds.
  • the reaction solution (E-14) obtained by the above method is coated on a corona-treated PET film having an area of 5 cm 2 and a thickness of 200 ⁇ m using a wire bar coater, and dried at room temperature for 24 hours (E-14)
  • the optical measurement of the PET substrate having the dried coating film of (E-14) shows that the average reflectance at a wavelength of 450 to 650 nm is 2.68%, and the minimum reflectance at a wavelength of 350 nm to 800 nm is 2.10%. there were.
  • the average reflectance at a wavelength of 450 to 650 nm is 4.32%, and the minimum reflectance at a wavelength of 350 nm to 800 nm is 3.3. It was 41%.
  • Optical measurement of this PET substrate having the dried coating of (E'-2) showed an average reflectance of 4.29% at a wavelength of 450 to 650 nm and a minimum reflectance of 3.23% at a wavelength of 350 nm to 800 nm. Met.
  • Optical measurement of this PET substrate having the dried coating of (E'-3) showed an average reflectance of 4.28% at a wavelength of 450 to 650 nm and a minimum reflectance of 3.14% at a wavelength of 350 nm to 800 nm. Met.
  • Optical measurement of this PET substrate having the dried coating of (E′-4) showed an average reflectance of 4.45% at a wavelength of 450 to 650 nm and a minimum reflectance of 3.38% at a wavelength of 350 nm to 800 nm. Met.
  • the average reflectance at a wavelength of 450 to 650 nm was 4.21%, and the minimum reflectance at a wavelength of 350 nm to 800 nm was 3.62%.
  • reaction liquid (B-7) 3.5 g of a 1.0% aqueous solution of PVA 235 (Kuraray, polyvinyl alcohol) was added to the obtained reaction liquid (B-7) while stirring with a magnetic stirrer, and the mixture was stirred for 10 minutes, aggregation Precipitation occurred.
  • the anionic particle (a-1) aqueous dispersion prepared in Reference Example 1 with the micromixer and the cationic particle (b-3) aqueous dispersion prepared in Reference Example 5 are each 5.0 mL / min using a syringe pump
  • the silica-coated gold particles (A-1s) prepared in Reference Example 7 were stirred with a magnetic stirrer by using a magnetic stirrer to stir the mixture, which was supplied from a silicone tube supplied with an inner diameter of 1 mm and a length of 106 mm.
  • the reaction mixture (C'-8) was obtained by dropping the solution into 100 mL of the aqueous dispersion for 50.0 seconds.
  • reaction solution (C′-8) 100 ml of the reaction solution (C′-8) was charged into a reactor equipped with a reflux condenser, a dropping tank, a thermometer and a stirrer, and the temperature in the reaction vessel was heated to 80 ° C.
  • a reflux condenser 100 ml of the reaction solution (C′-8) was charged into a reactor equipped with a reflux condenser, a dropping tank, a thermometer and a stirrer, and the temperature in the reaction vessel was heated to 80 ° C.
  • 0.5 g of aminopropyltrimethoxysilane diluted to 0.1% by mass with ethanol was added, reacted for 5 minutes, and then 2.0 g of tetraethoxysilane diluted to 1% with ethanol was added over 30 minutes
  • the solution was dropped, and the temperature in the reaction vessel was kept at 80 ° C., and stirring was continued for about 6 hours. Thereafter, the reaction solution was cooled to room temperature to obtain a reaction solution (
  • reaction liquid (F'-8) 3.5 g of a 1.0% aqueous solution of PVA235 (Kuraray, polyvinyl alcohol) 1.0% aqueous solution is added to the obtained reaction liquid (F'-8) while stirring with a magnetic stirrer, and a gold particle cyclic structure-containing PVA aqueous solution I got (E'-8).
  • the reaction solution (E'-8) obtained by the above method is coated on a corona-treated PET film having an area of 5 cm 2 and a thickness of 200 ⁇ m using a wire bar coater, and dried at room temperature for 24 hours (E ') A PET substrate coated with the dried coating film of -8) was obtained.
  • Optical measurement of this PET substrate having the dried coating of (E'-8) showed an average reflectance of 3.81% at a wavelength of 450 to 650 nm and a minimum reflectance of 3.12% at a wavelength of 350 nm to 800 nm. Met.
  • a novel metal particle annular structure as a nanometer scale resonator structure which can function as a metamaterial three-dimensionally, an insulating coated metal particle annular structure value, and a composition. .

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Abstract

La présente invention concerne la fourniture d'une nouvelle structure annulaire de particules métalliques capable de fonctionner en trois dimensions en tant que métamatériau. Cette structure annulaire de particules métalliques (C) est caractérisée en ce qu'elle comprend : un support isolant (B) composé d'une structure de connexion de particules dans laquelle une pluralité de particules sont connectées ; et une pluralité de particules métalliques (A) disposées de manière annulaire autour du support isolant (B).
PCT/JP2018/034299 2017-09-15 2018-09-14 Structure annulaire de particules métalliques, structure annulaire de particules métalliques revêtues d'isolant et composition Ceased WO2019054508A1 (fr)

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KR1020207006853A KR102296364B1 (ko) 2017-09-15 2018-09-14 금속 입자 고리형 구조체, 절연재 피복 금속 입자 고리형 구조체 및 조성물
EP18857014.7A EP3682986B1 (fr) 2017-09-15 2018-09-14 Structure annulaire de particules métalliques, structure annulaire de particules métalliques revêtues d'isolant et composition
US16/646,569 US11352504B2 (en) 2017-09-15 2018-09-14 Metal particle annular structure, insulator-coated metal particle annular structure, and composition
JP2019542325A JP6938651B2 (ja) 2017-09-15 2018-09-14 金属粒子環状構造体、絶縁材被覆金属粒子環状構造体、及び組成物
CA3075792A CA3075792C (fr) 2017-09-15 2018-09-14 Structure annulaire de particules metalliques, structure annulaire de particules metalliques revetues d'isolant et composition
CN201880055121.2A CN111065473B (zh) 2017-09-15 2018-09-14 金属颗粒环状结构体、被覆有绝缘材料的金属颗粒环状结构体以及组合物

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CN111065473A (zh) 2020-04-24
EP3682986B1 (fr) 2025-11-12
CA3075792A1 (fr) 2019-03-21
CA3075792C (fr) 2022-10-04
JPWO2019054508A1 (ja) 2020-04-16
EP3682986A1 (fr) 2020-07-22
US11352504B2 (en) 2022-06-07
US20200263039A1 (en) 2020-08-20
CN111065473B (zh) 2022-04-19

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